US3423443A - Fluoroalkyltin compounds - Google Patents

Fluoroalkyltin compounds Download PDF

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US3423443A
US3423443A US474481A US3423443DA US3423443A US 3423443 A US3423443 A US 3423443A US 474481 A US474481 A US 474481A US 3423443D A US3423443D A US 3423443DA US 3423443 A US3423443 A US 3423443A
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Walter Blochl
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FMC Corp
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • C07F7/2224—Compounds having one or more tin-oxygen linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/12—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing tin

Definitions

  • Y is hydrogen or lower alkyl
  • X is chlorine, bromine, iodine, alkoxy, acyl, hydrogen, siloxyl or stannoxyl
  • Q is oxygen or sulfur; R is lower alkyl; R, is
  • the present invention relates to fiuoroalkyltin compounds, the method of their preparation, and their use as antiadhesive and oil-repellent impregnating agents.
  • Antiadhesive and oil-repellent impregnating agents for textiles of every type, for paper, wood, leather, ceramic surfaces, glass surfaces, and plastic surfaces, such as for example varnishes or articles made of polyester, are being required in ever increasing degrees.
  • the substances primarily available for this purpose are silicones or fluorocarbon resins for dirt-repellent and oil-repellent impregnation.
  • fluorocarbon resins it is often difficult to use fluorocarbon resins as emulsions, since they are of limited stability, or have other disadvantages such as discoloration, damage to the fiber to which they are applied, inferior resistance to laundering, and the like.
  • fluoroalkyltin compounds which contain only hydrogen or alkyl radicals in the aand fl-positions to the tin are excellent impregnating agents for the type of materials mentioned above, and that they do not possess many of the disadvantages of the substances heretofore used for this purpose.
  • the compounds of the above-described class are for the most part extremely stable and generally can be used in the form of homogeneous solutions. Aftertreatment, for example by heating, is not essential. Resistance to laundering is very good, and discoloration does not occur. Accordingly, these solutions are particularly well suited for use in aerosol dispensers by individual consumers.
  • the compounds of this invention include especially the following types, wherein oxygen may partly or wholly be replacedwith sulfur:
  • hydrogen in the alkyl chain may be replaced by lower alkyl radicals such as for example methyl, ethyl, propyl, butyl and amyl
  • X is a halogen selected from the group consisting of chlorine, bromine and iodine, alkoxy, acyl, hydrogen, siloxyl or stannoxyl
  • R is CF (CF,),,,--, CF Cl(CF or CF H(CF where m is 4 to 25 and preferably 5 to 16; R is lower alkyl; n is 2 to 8 and preferably 2 to 3, and p designates a polymer.
  • polystannosiloxanes of linear or crosslinked polymer structure which are readily .obtained by cocondensation or cohydrolysis, whose structures are characterized by the following general formulae:
  • R R and R are methyl, ethyl or R;(CH R is R,(CH where n is 2 to 8 and preferably 2 to 3, and H may be replaced with methyl; x is 1 to 20; and y is l to 20.
  • These polymers are also obtained by reacting the corresponding alkoxy silanes with the corresponding fluoroalkyltin acetates R Sn(OOC-CH or Sn(OOCCHa)t Ra
  • the latter method is particularly suitable for producing crosslinked stannosiloxanes in situ on textile and leather materials.
  • such resins have a protective fungicidal effect for the substrate which is of special advantage for leather, wood and textiles.
  • the low toxicity of these fungicidal resins as compared with their nonfiuorinated homologues is especially advantageous in the case of textiles.
  • the fiuoroalkyltin compounds of this invention may be produced in accordance with the following methods.
  • the tetraalkyl stannanes can be prepared directly and reduced. They can then be produced by disproportionating according to Kocheshkow in the manner which is known in connection with nonfiuorinated alkyl stannanes or fiuoroalkyltin chlorides comprises the in this regard. The resulting yields are above 80% based upon the Grignard compound.
  • the second possible method of producing fiuoroalkyl stannes or fiuoroalkyltin chlorides comprises the use of the method proposed by Harada in Sci. Pap. Inst. Physic. Chem. Res. (Tokyo) 35, 290 (1939), Gottblatt (1939) II, 2912, when the reaction is carried out, in a generally known manner with tin alloys of metals of the first to third group of the Periodic Table such as tinalkali or tin-sodium-zinc alloys:
  • a third generally known process may also be used for the production of fiuoroalkylstannanes.
  • Olefins or acetylenes carrying a perfluoro-higher-alkyl chain are very easily added to tin hydrides or alkyl tin hydrides, whereby adding small amounts of azobis(isobutyronitrile) (AIBN) and heating to temperatures between 50 and 70 C. results not only in an ionic reaction, but also preferably in a radical reaction.
  • Ultraviolet light is also very effective. The yields are in excess of 90%; the conversions are very high. Equimolar amounts of the reactants are used:
  • the fiuoro olefins suited for this purpose are exclusively olefins which are not fiuorinated on the double bond, so that stannanes are formed which have only hydrogen or alkyl radicals in the land Z-positions of the alkyl portion. Only such compounds are hydrolysisstable and are suitable for use for permanent impregnation.
  • the following olefins and acetylenes are especially suitable:
  • This reaction mixture is advantageously reacted with sodium methoxide which converts it into the ortho-stannonic esters.
  • these esters When dissolved in trichloroethylene, these esters can be used to impregnate a substrate. After drying and possibly curing, a washproof, oleophobic and fungicidal impregnating effect is obtained.
  • Another novel method consists in the addition of perfluoroiodoalkane, w-chloroperfluoroidoalkane and w-hydrogen-perfiuoroiodoalkane to unsaturated organic tin compounds according to radical or thermal reaction.
  • the reaction is thermally initiated by heating at 150- 220 C. for one or more hours, at 220-300 C. for less than one hour and preferably for less than 20 minutes, or at temperatures in excess of 300 C. for less than 10 minutes and preferably for 40 seconds.
  • the reaction may be carried out in liquid phase under pressure or in vapor phase under elevated, normal or reduced pressure.
  • the readily available vinyl, allyl, propargyl, ethinylstannanes and the corresponding chlorostannanes are the preferred unsaturated tin compounds. Yields are mostly in excess of
  • the resulting fiuoroiodoalkyltin compounds can advantageously be freed of iodine with reducing agents, the compounds being preferably shaken with aqueous sodium bisulfite solution or other reducing agents, or the iodine in the fiuoroalkylstannane being replaced with hydrogen by means of zinc or palladiumactivated zinc, in aqueous, strongly hydrochloric solution or in glacial acetic acid.
  • CH(CHD
  • the fiuorinated tetraalkyltins may be reacted with tin tetrahalide in the desired ratio by heating for several minutes to 200 C. thereby disproportionating according to Kosheshkow, possibly by adding a Lewis acid catalyst, such as aluminum chic-- ride or zinc chloride (British Patent 739,883).
  • a Lewis acid catalyst such as aluminum chic-- ride or zinc chloride
  • stannonic and thiostannonic acids which are prepared from fluoroalkyltin trichlorides and which are obtained by saponification, in a manner known per se, with alkalies or alkali sulfides (Ber. 36, 1057 (1903), and 62, 997 (1920), or their esters are eminently suitable in solutions of trichloroethylene and ethanol for impregnating textiles, leather, wood, and other substances by dipping and squeezing, or spraying, or brushing, and subsequently drying.
  • the impregnating agent may be fixed especially strongly by heating to about 80440 C.
  • the surfaces or porous-fibrous substances thus treated are thus made oil-repellent and hydrocarbon-repellent.
  • oil-repellent and hydrocarbon-repellent For example, gasoline and parafiin oil will flow off in the form of beads.
  • the fabrics can be cleaned easily. Suede is no longer so sensitive to stains. varnished surfaces of cars can be cleaned more easily.
  • a conventional impregnating agent contains dialkyltin compounds, the mixed-condensate of siloxane and stannonic acid imparts to the substrate fungicidal properties.
  • EXAMPLE 1 Twelve grams of vinyltin trichloride additionally containing divinyltin dichloride were dissolved in 20 g. of diisopropyl ether, to which 33 g. of perfluorodecyl iodide were added. This mixture was irradiated with a 500 watt ultraviolet lamp for 48 hours while being stirred in a Pyrex tube, and while the contents of the Pyrex tube were cooled by means of an air jet. This reaction mixture was added drop by drop with cooling and stirring into 100 cc. of methanol in which 8 g. of sodium methoxide were dissolved. The sodium chloride was filtered off. The filtrate was dissolved in 1000 cc.
  • Tetravinyltin (2.83 g.) was dissolved in 22 g. of perfluorooctyl iodide.
  • the reaction mixture was irradiated, in a liquid layer 2 mm. thick, with a 500 watt mercury vapor high-pressure lamp. Cooling with air prevented the temperature from rising too high, and stirring by means of a magnetic stirrer provided a good liquid exchange at the layer of irradiation. The use of extremely pure nitrogen prevented access of oxygen to the Pyrex irradiation vessel.
  • the reaction was completed after 12 hours. According to gas-chromatographic analysis, the reaction mixture contained only 5% perfluoroalkyl iodide. The entire reaction mixture was mixed with 5.5 g.
  • EXAMPLE 3 One gram of the irradiated reaction product of Example 1 containing 6 CmFmCHzCH'ISHClg and (C 0Fg1cHgCHI)gSnCig was added, drop by drop, to 20 cc. of methanolic sodium methoxide containing mg. of sodium. The mixture was stirred well and cooled. The precipitated sodium chloride was decanted, and this solution was then vigorously shaken for 1 hour with 10 g. of 0.5% sodium amalgam. The amalgam was then separated, and the solution was mixed with 20 cc. of trichloroethylene and strongly acidified with concentrated aqueous hydrochloric acid.
  • the heavier trichloroethylene phase was separated and washed again with 20% aqueous HCl.
  • the mixture containing CloFglCHgCHZSD 3 was diluted with 40 cc. of trichloroethylene and then used to impregnate a linen cloth, which was then dried at C.
  • the solution was decanted and mixed with twice its volume of trichloroethylene.
  • the mixture was then shaken with about 50 cc. of 25% aqueous hydrochloride acid, the separated trichloroethylene solution was washed again with 30 cc. of 25% hydrochloric acid, and dried over sodium sulfate.
  • the solution is neutralized with aqueous methanolic sodium methoxide solution. The sodium chloride was decanted.
  • EXAMPLE 7 Ten cubic centimeters of the solution prepared in Example 6 were mixed with 0.3 of pyridine, and a filter paper was dipped into the mixture. The filter paper was cured in the dryer at 120 C. for 10 minutes. In contrast to a nontreated comparative piece of paper, the treated paper did not become dirty, even when touched frequently with slightly dirty hands.
  • EXAMPLE 8 A polyester boat shell was coated with the solution described in Example 3, whereupon the boat was exposed to strong sun rays. After five hours, the plastic boat was launched in water. Even after the boat had been in contaminated water for several days, there was no dirt ring along the water line which could not be removed by simple wiping, whereas a nontreated boat had on obstinately adhering dirt ring.
  • EXAMPLE 10 A mixture consisting of 30 percent by weight of vinyltin trichloride and 70 percent of l-iodoperfiuorooctane was pressed at a speed of 25 g./min. through a Hastelloy C tube having an inside diameter of 4 mm. and a length of 1 m. "by means of a high-pressure metering pump. The temperature of the reaction tube was maintained at 300 C. After a residence time of about 50 seconds, the reaction mixture was depressurized from 200 atm. to atmospheric pressure by way of a pressure valve and was introduced into ethanol.
  • C1QFMCHQCH3SD was used to impregnate pieces of linen cloth, cotton poplin and fabric made of polyester fiber, as well as a piece of suede, paper, a roll of yarn, and a piece of cellophane film. After being dried at temperatures between C. and 120 C. for 20 mintues, all substrates thus treated became strongly oil-, water-, dirt-, and adhesiverepellent; oil and gasoline flowed off these substrated in the form of beads.
  • EXAMPLE l2 Thirty-three grams of vinyltin trichloride were mixed with g. of l-iodo-lo-chloroperfluorodecane, and were irradiated for 17 hours in a layer 2 mm. thick at a distance of 5 cm. with a 500 watt mercury vapor lamp while being cooled with air. The reaction mixture was then dissolved in 900 cc. of ethanol and was shaken for 1 hour with an abundant amount of 0.5% sodium amalgam. The solution was then separated from the reducing agent, processed according to the procedure set forth in Example 11, and the resulting solution containing pCHgCHzSH (OC H 3 was used for impregnating cotton poplin and a piece of filter paper. After being dried at C. for 10 minutes, the substrates containing had a strongly oleophobic and hydrophobic character.
  • EXAMPLE 14 Three hundred cubic centimeters of the alcohol solution obtained according to Example 11 after being treated with the ion exchange resin, were added drop by drop with stirring to 80 cc. of a 5% caustic soda solution; the resulting emulsion was diluted with 1200 cc. of water. This solution containing the sodium salt of was used to impregnate a piece of linen cloth, a piece of filter paper and a roll of synthetic yarn; these substrates were dried in the air at normal temperature. After several hours, the substrates which were neutralized with dilute acetic acid had a strong oleophobic property. They repelled eyclohexane in the form of beads.
  • EXAMPLE 15 Three hundred cubic centimeters of the solution obtained according to Example 12 was stirred for 5 hours, after reduction, with 100 cc. of dehydrated, methanol soaked, chloride-charged, strongly basic Dowex -2-X8 anion exchange resin and then decanted. This solution was diluted with 200 cc. of an aqueous 4% sodium sulfide solution, and then with 1000 cc. of water. The solution prepared in this manner containing was used to impregnate a piece of textile fabric made of viscose staple, a piece of cotton fabric and a piece of filter paper. The substrates were dried at 100 C. and then hardened by being heated with a hot iron. All pieces thus impregnated with repelled oil, gasoline, heptane and water and were dirtand adhesive-repellent.
  • EXAMPLE 16 17 g. of vinyltin trichloride, 9 g. of divinyltin dichloride and 9 g. of dibutyltin dichloride were mixed with 100 g. of l-iodoperfiuorodecane and irradiated in a 2 mm. layer with a 500 watt ultraviolet mercury vapor lamp for 12 hours. This reaction mixture was carefully added drop by drop to 300 cc. of ethanol and shaken with 10 g. of zinc turnings for 1 hour.
  • the solution containing c r cn cn smcrm) 1% was diluted with trichloroethylene and used for the impregnation of textiles by soaking, drying, and heating at 120 C. for a short time. All substrates treated in this manner contained and showed strong oiland water-repellent characteristics.
  • EXAMPLE 17 The alcohol solution of the ortho-ethyl ester of fluoroalkylstannonic acid obtained according to Example 16 was slowly passed through a column of dehydrated, chloride-charged Dowex 2X8 anion exchange resin which had been soaked with ethanol. The resulting iodide-free solution containing was diluted to a concentration of 3% and then used for impregnating textiles and leather. The resulting substrates had strong oiland water-repellent characteristics.
  • EXAMPLE 18 cc. of the iodide-free alcohol solution obtained according to Example 17 was added drop by drop with stirring to 60 cc. of a 10% aqueous sodium hydroxide solution. The resulting emulsion containing was then diluted with 900 cc. of water and used to impregnate a thoroughly washed fabric containing a mixture of cotton and viscose staple, a cellophane film and a piece of linen; these substrates were squeezed out, dried and heated to C., and treated with carbon dioxide gas, whereupon the alkalies were washed out with water. The substrates treated in this manner contained.
  • EXAMPLE 19 Ten grams of vinyltin trichloride together with 30 g. of l-iodoperfluorododecane were dissolved in 60 g. of diisopropyl ether under exclusion of oxygen and intensive cooling and irradiated under stirring for 20 hours in a layer 5 mm. thick with a 1000 watt mercury high-pressure vapor lamp from a distance of 10 cm. A vigorous stream of hydrogen sulfide was then passed through the. reaction mixture for two hours, the temperature being" raised slowly to 50 C. The lost ether was replaced with methylchloroform. This solution was again briefly shaken with H s-saturated water for removing the hydrohalic acids and then dried over sodium sulfate.
  • EXAMPLE 20 metal had been separated, 200 cc. of carbon tetrachloride were added, and the mixture was shaken with water. The resulting dried carbon tetrachloride solution of fluoroalkylstannane was concentrated by evaporation until all of the carbon tetrachloride was distilled off. The resulting stannane was dissolved in 11 g. of tin tetrachloride while heating under reflux, and stirred for 8 hours at temperatures up to 110 C. while excluding moisture. In order to accelerate the reaction, AlCl was added.
  • This reaction mixture containing was used directly in an inert solvent such as methyl chloroform, or in a methanol, glycol, or polyglycol solution for impregnating textiles, fiber mats and yarns of all kinds and regenerated cellulose.
  • the substrates were moistened with diluted solutions of about 1 to 5% concentrations and dried. Where necessary, they were subsequently neutralized with ammonia and heated to 120 C. for 5 minutes. All substrates impregnated in this manner had a pronounced oiland water-repellent character.
  • EXAMPLE 21 Three grams of tetravinyltin and 28 g. of l-iodo-8- hydroperfluorooctane were dissolved in 60 g. of acetone and irradiated with a 300 watt mercury high-pressure immersion lamp under strong cooling and stirring. After 10 hours, the acetone was distilled out of this reaction mixture; after 200 cc. of isopropanol had been added, the mixture was shaken for 1 hour with an abundant amount of 0.2% sodium amalgam for de-iodination. After the metal had been separated, 200 cc. of carbon tetrachloride were added, and the mixture was shaken with water.
  • the resulting dried carbon tetrachloride solution of fluoroalkylstannane was concentrated by evaporation until all of the carbon tetrachloride was distilled off.
  • the resulting stannane was dissolved in 11 g. of tin tetrachloride while heating under reflux, and stirred for 8 hours at temperatures up to 110 C. while excluding moisture.
  • ZnCl was added. This reaction mixture containing was used directly in an inert solvent such as methyl chloroform, or in a methanol, glycol, or polyglycol solution for impregnating textiles, fiber mats and yarns of all kinds and regenerated cellulose.
  • the substrates were moistened with diluted solutions of about 1 to 5% concentration and dried. Where necessary, they were subsequently neutralized with sodium bicarbonate solution and heated to 120 C. for 5 minutes. All substrates impregnated in this manner had a pronounced oiland waterrepellent character.
  • EXAMPLE 23 Three grams of tetravinyltin were reacted with 25 g. of l-iodoperfluorohexane and then treated as described in Example 20. Instead of using acetone, diisopropyl ether was used. The resulting C,F ,CH,CH,SnCl was heated under reflux with 40 g. of acetic acid. The resulting C FuCHgCHgSH 3 was used in 0.5 to 5% methyl ethyl ketone solutions for the oil-repellent impregnation of textiles by simple dipping and drying, and as mold release agent for rubber vulcanizing and plastic molds. Cellophane and polyethylene films became strongly anti-adhesive after being treated with such solutions.
  • EXAMPLE 24 Ten grams of the fluoroalkyltin triacetate, obtained according to Example 22 were dissolved in 40 g. of methyl isobutyl ketone to which 5 g. of dimethyldiethoxysil ane were added, and the mixture was applied t a cotton fabric, a polyester sewing thread, a flat-headed screw for wood, and a flat iron. After these articles had been heated briefly, they showed a strongly dirt-repellent character. The screws were strongly anti-adhesive, and it was therefore much easier to screw them into moisture wood. The iron did not absorb starch residues from the laundry being ironed, whereas starch residues stuck to the bottom of the iron when it was not treated.
  • EXAMPLE 25 Ten grams of fluoroalkyltin trichloride produced according to Example 20 were reacted with a mixture of 20 g. of acetylacetone and 20 g. of butanol. This acidic solution was neutralized with a small amount of aqueous caustic soda solution and, after mg. of perfiuorooctanoic acid ammonium salt had been added, was emulsified in an Ultraturrax blender in 30 g. of water. This emulsion containing was diluted with an additional amount of water and used, in 0.3 to 3% dilution, as mold release agent and for the oil-repellent impregnation of textiles and paper.
  • the substrates were saturated in said emulsion, dried and heated to C. for 10 minutes.
  • the substrates contained CF CI(CF,)',CH,CH,Sn(O)OSn(0) CH,CH CF 7C1: Cl and repelled oil, gasoline and water.
  • EXAMPLE 26 One hundred-sixty grams of diallyl, together with 9 g. of butyltin trihydride, were slowly heated in 100 g. of diisopropyl ether at 50 to 60 C. under stirring for 8 hours, at the start of which 1 g. of azobis(isobutyronitrile) was added, and 0.5 g. of the same compound were added every 2.5 hours thereafter. The operation was carried out under the exclusion of oxygen. The excess diallyl and the solvent were distilled out of this mixture. After 120 g. of l-iodoperfluorodecane and 200 g. of diisopropyl ether had been added, the reaction mixture was heated at 70 C. under exclusion of oxygen, 1 g.
  • EXAMPLE 27 200 g. of diallyl ether, together with 9 g. of butyltin trihydride, were slowly heated in 100 g. of diisopropyl ether at 50 to 60 C. under stirring for 8 hours, at the start of which 1 g. of azobis(isobutyronitrile) was added, and 0.5 g. of the same compound are added every 2.5 hours thereafter. The operation was carried out under the exclusion of oxygen. The excess diallyl ether and the solvent were distilled out of this mixture. After 120 g. of l-iodoperfluorodecane and 200 g. of diisopropyl ether had been added, the reaction mixture was heated at 70 C. under exclusion of oxygen, 1 g.
  • EXAMPLE 28 Nine grams of butyltin trihydride together with 110 g. of CH CH(CF,) CF are heated, in 200 cc. of diisopropyl ether, for 6 hours at 50 to 60 C., while a total of 2 g. of azobis(isobutyronitrile) was added continuously. After the solvent had been distilled off, 40 g. of tin tetrachloride and 0.1 g. of AlCl were added. The mixture was heated to 110 C. under stirring for 6 hours. The resulting mixture containing was used in alcoholic solution as impregnating agent for textiles.
  • EXAMPLE 29 Nine grams of butyltin trihydride together with 90 g. of HCC(CF CF are heated, in 200 cc. of diisopropyl ether, for 6 hours at 50 to 60 C., 'while a total of 2 g. of azobis(isobutyronitrile) was added continuously. After the solvent had been distilled off, 40 g. of tin tetrachloride and 0.1 g. of AlCl were added. The mixture was heated to 110 C. under stirring for 6 hours. The resulting fluoroalkylchlorostannane mixture was used directly as impregnating agent for textiles.

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Cited By (4)

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US3522206A (en) * 1966-11-09 1970-07-28 Noury & Van Der Lande Process of stabilizing polyvinyl chloride resins and the product
US3542824A (en) * 1968-07-31 1970-11-24 Dow Chemical Co Perfluorocarboxylic acid ester of tricyclohexyltin hydroxide
US3861802A (en) * 1973-07-02 1975-01-21 Continental Oil Co An improved turbidimeter lens for reducing the tendency of mixtures of immiscible fluids to form films of the lenses
FR2824560A1 (fr) * 2001-05-09 2002-11-15 Saint Gobain Compose pour le traitement hydrophobe de vitrages, procede pour l'obtenir

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US2682512A (en) * 1948-08-02 1954-06-29 Minnesota Mining & Mfg Unsaturated organosilanes and method of making same
US2800494A (en) * 1954-10-22 1957-07-23 Dow Corning Unsaturated fluorocarbon silanes and their hydrolysis products
GB926282A (en) * 1958-05-17 1963-05-15 Philips Nv Improvements in or relating to organo-tin compounds for combating micro-organisms
GB933365A (en) * 1960-10-05 1963-08-08 Basf Ag Production of haloalkyltin(iv) halides
US3338943A (en) * 1963-05-13 1967-08-29 Dow Corning Aminoorganosiloxane-carboxyorganosiloxane copolymers

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Publication number Priority date Publication date Assignee Title
US2682512A (en) * 1948-08-02 1954-06-29 Minnesota Mining & Mfg Unsaturated organosilanes and method of making same
US2800494A (en) * 1954-10-22 1957-07-23 Dow Corning Unsaturated fluorocarbon silanes and their hydrolysis products
GB926282A (en) * 1958-05-17 1963-05-15 Philips Nv Improvements in or relating to organo-tin compounds for combating micro-organisms
GB933365A (en) * 1960-10-05 1963-08-08 Basf Ag Production of haloalkyltin(iv) halides
US3338943A (en) * 1963-05-13 1967-08-29 Dow Corning Aminoorganosiloxane-carboxyorganosiloxane copolymers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3522206A (en) * 1966-11-09 1970-07-28 Noury & Van Der Lande Process of stabilizing polyvinyl chloride resins and the product
US3542824A (en) * 1968-07-31 1970-11-24 Dow Chemical Co Perfluorocarboxylic acid ester of tricyclohexyltin hydroxide
US3861802A (en) * 1973-07-02 1975-01-21 Continental Oil Co An improved turbidimeter lens for reducing the tendency of mixtures of immiscible fluids to form films of the lenses
FR2824560A1 (fr) * 2001-05-09 2002-11-15 Saint Gobain Compose pour le traitement hydrophobe de vitrages, procede pour l'obtenir

Also Published As

Publication number Publication date
DE1469252A1 (de) 1968-12-19
BE667480A (de) 1965-11-16
AT266862B (de) 1968-12-10
CH448963A (de) 1968-04-11
AT265311B (de) 1968-10-10
CH1045865A4 (de) 1967-09-15
AT278695B (de) 1970-02-10
NL6509546A (de) 1966-01-31

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